JP2020132739A - Die-bonding silicone resin composition, cured product, and light-emitting diode element - Google Patents

Abstract

To provide a die-bonding silicone resin composition, that yields a cured product of high hardness and that has no contamination of gold pad.SOLUTION: The die-bonding silicone resin composition is one, containing (A) a specific linear organopolysiloxane, (B) a specific branched organopolysiloxane, (C) a specific linear or cyclic organohydrogenpolysiloxane, and (D) a platinum group metal-based catalyst, each in a specific amount, and in which, when cured at 100°C for 1 hour and further at 150°C for 2 hours, the volatile matter is 1.5 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a silicone resin composition for die bonding such as a light emitting diode element, a cured product, and a light emitting diode element.

It has been proposed to use a silicone resin as a die bond material for a light emitting diode (hereinafter referred to as "LED") element (Patent Documents 1 to 3). Silicone resins are mainly used for blue LEDs and white LEDs because they are superior in heat resistance, weather resistance, and discoloration resistance to conventional epoxy resins.
On the other hand, in a die bond material using a silicone resin, a problem has been reported in which the gold pad of an LED element is contaminated with low molecular weight siloxane. If the gold pad is heavily contaminated, problems such as subsequent wire bonding cannot occur.

Japanese Unexamined Patent Publication No. 2006-342200 Japanese Unexamined Patent Publication No. 2015-93970 Japanese Unexamined Patent Publication No. 2018-150493

The present invention has been made in view of the above problems, and an object of the present invention is to provide a silicone resin composition for die bonding, which provides a cured product having a high hardness and does not contaminate the gold pad during curing.

In order to achieve the above problems, the present invention
(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a viscosity at 25 ° C. of less than 100 mPa · s.
(B) Branched organopolysiloxane represented by the following average unit formula (1) and waxy or solid at 25 ° C.: (B) with respect to a total of 100 parts by mass of the components (A) and (B). Amount of ingredients 50-90 parts by mass,
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ¹ R ² SiO) _n (R ² ₂ SiO) _p (R ¹ SiO _3/2 ) _q (R ² SiO) _3/2 ) _r (SiO _4/2 ) _s (1)
(In the formula, R ¹ independently represents an alkenyl group and R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, at least 80 of all R ² . Mol% is a methyl group and l, m, n, p, q, r and s are l ≧ 0, m ≧ 0, n ≧ 0, p ≧ 0, q ≧ 0, r ≧ 0 and s, respectively. It is a number that satisfies ≧ 0, m + n + q> 0, q + r + s> 0, and satisfies l + m + n + p + q + r + s = 1.)
Represented by (C) the following average compositional formula (2), having at least two SiH bonds per molecule, and, (C) more than 20% of _{SiO 2/2} units in component ^R ₃ 2 SiO Linear or cyclic organohydrogenpolysiloxane which is _2/2 unit: SiH bond in component (C) is 0.5 to 5 for one silicon atom-bonded alkenyl group in component (A) and component (B). Amount of 0.0 pieces,
R ³ _a H _b SiO _{(4-ab) / 2} (2)
(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, and at least 50 mol% of the total R ³ is a methyl group, and a and b is a number that satisfies 1.2 ≦ a ≦ 2.1, 0.1 ≦ b ≦ 1.0, and 1.6 ≦ a + b ≦ 2.4), and (D) a platinum group metal-based catalyst. : Contains an amount of 1 to 500 ppm in terms of mass of metal atoms with respect to the total of the components (A) to (C).
Provided is a silicone resin composition for die bonding having a volatile content of 1.5% by mass or less when cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours.

Since the silicone resin composition for die bonding of the present invention provides a cured product having a high hardness with a small amount of volatile matter during curing, there is no risk of contamination of the gold pad, and it is suitable for die bonding of LED elements and the like. It is particularly useful as a die bond material used.

The present invention also provides a cured product obtained by curing the above-mentioned silicone resin composition for die bonding.
The cured product of the present invention has a high hardness.

Furthermore, the present invention provides a light emitting diode element that is die-bonded with the cured product.
The light emitting diode element of the present invention is highly reliable and is die-bonded with a cured product having high hardness.

The silicone resin composition for die bonding of the present invention has a small amount of volatile matter during curing and gives a cured product having high hardness. Therefore, the gold pad is not contaminated and is used for die bonding of LED elements and the like. It is particularly useful as a die bond material.

As described above, there has been a demand for the development of a silicone resin composition for die bonding, which provides a cured product having a high hardness and does not contaminate the gold pad.

As a result of diligent studies on the above problems, the present inventors have made a silicone resin composition for die bonding containing a specific amount of the following components (A) to (D) and having a volatile content of a certain amount or less at the time of curing. If so, we have found that the above problems can be solved and completed the present invention.

That is, the present invention
(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a viscosity at 25 ° C. of less than 100 mPa · s.
(B) Branched organopolysiloxane represented by the following average unit formula (1) and waxy or solid at 25 ° C.: (B) with respect to a total of 100 parts by mass of the components (A) and (B). Amount of ingredients 50-90 parts by mass,
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ¹ R ² SiO) _n (R ² ₂ SiO) _p (R ¹ SiO _3/2 ) _q (R ² SiO) _3/2 ) _r (SiO _4/2 ) _s (1)
(In the formula, R ¹ independently represents an alkenyl group and R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, at least 80 of all R ² . Mol% is a methyl group and l, m, n, p, q, r and s are l ≧ 0, m ≧ 0, n ≧ 0, p ≧ 0, q ≧ 0, r ≧ 0 and s, respectively. It is a number that satisfies ≧ 0, m + n + q> 0, q + r + s> 0, and satisfies l + m + n + p + q + r + s = 1.)
Represented by (C) the following average compositional formula (2), having at least two SiH bonds per molecule, and, (C) more than 20% of _{SiO 2/2} units in component ^R ₃ 2 SiO Linear or cyclic organohydrogenpolysiloxane which is _2/2 unit: SiH bond in component (C) is 0.5 to 5 for one silicon atom-bonded alkenyl group in component (A) and component (B). Amount of 0.0 pieces,
R ³ _a H _b SiO _{(4-ab) / 2} (2)
(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, and at least 50 mol% of the total R ³ is a methyl group, and a and b is a number that satisfies 1.2 ≦ a ≦ 2.1, 0.1 ≦ b ≦ 1.0, and 1.6 ≦ a + b ≦ 2.4), and (D) a platinum group metal-based catalyst. : Contains an amount of 1 to 500 ppm in terms of mass of metal atoms with respect to the total of the components (A) to (C).
A silicone resin composition for die bonding having a volatile content of 1.5% by mass or less when cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In the present specification, "Me" represents a methyl group and "Vi" represents a vinyl group.

<Silicone resin composition for die bonding>
Hereinafter, each component will be described in more detail.
[(A) component]
The component (A) has at least two alkenyl groups bonded to silicon atoms in one molecule and has a viscosity at 25 ° C. of less than 100 mPa · s (preferably 1 mPa · s or more and less than 100 mPa · s, more preferably. It is a linear organopolysiloxane (5 to 60 mPa · s). When the viscosity exceeds 100 mPa · s, it becomes difficult to obtain the target high hardness because this component acts as a soft segment more than necessary, and there arises a problem that the viscosity of the composition becomes remarkably high.

The alkenyl group bonded to the silicon atom is preferably a vinyl group, an allyl group, an ethynyl group or the like having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.

The alkenyl group bonded to the silicon atom may be present at either the terminal chain or the side chain of the molecular chain in the molecule of the organopolysiloxane of the component (A), or may be present at both of them. However, it is preferable that it is present at least at both ends of the molecular chain.
The group bonded to the silicon atom other than the alkenyl group is not particularly limited as long as it does not have an addition-reactive carbon-carbon double bond, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. Alkyl groups such as hexyl group and heptyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, trill group, xsilyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl A group, an alkyl halide group such as a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc., usually has 1 to 12 carbon atoms, preferably 1 to 10, and more preferably 1 to 8. , Unsubstituted or halogen-substituted monovalent hydrocarbon groups, with methyl groups being particularly preferred.

The organopolysiloxane of the component (A) is preferably represented by the average composition formula (3), for example.
R ⁴ _d R ⁵ _e SiO _{(4-d-e) / 2} (3)
(In the formula, R ⁴ is independently an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon double bond, R ⁵ is independently an alkenyl group, and d is 1. The number of 9 to 2.1, e is a number of 0.005 to 1.0, and d + e satisfies 1.95 to 3.0.)

Addition reactive carbon represented by R ⁴ - The unsubstituted or substituted monovalent hydrocarbon group having no carbon-carbon double bond, the same ones as exemplified as the groups bonded to silicon atoms other than the alkenyl group Can be mentioned.

Examples of the alkenyl group represented by R ⁵ include those similar to those exemplified as the alkenyl group bonded to the silicon atom.
d is preferably a number of 1.95 to 2.00, e is preferably a number of 0.01 to 0.5, and d + e is preferably a number of 1.98 to 2.5.

Examples of the linear organopolysiloxane of the component (A) include those represented by the following formulas.
Vi (R ⁶ ) ₂ SiO [Si (R ⁶ ) ₂ O] _f Si (R ⁶ ) ₂ Vi
Vi (R ⁶ ) ₂ SiO [Si (R ⁶ ) ViO] _g [Si (R ⁶ ) ₂ O] _h Si (R ⁶ ) ₂ Vi
(Vi) ₂ R ⁶ SiO [Si (R ⁶ ) ₂ O] _f SiR ⁶ (Vi) ₂
(Vi) ₃ SiO [Si (R ⁶ ) ₂ O] _f Si (Vi) ₃
(Vi) ₂ R ⁶ SiO [Si (R ⁶ ) ViO] _g [Si (R ⁶ ) ₂ O] _h SiR ⁶ (Vi) ₂
(Vi) ₃ SiO [Si (R ⁶ ) ViO] _g [Si (R ⁶ ) ₂ O] _h Si (Vi) ₃
(R ⁶ ) ₃ SiO [Si (R ⁶ ) ViO] _g [Si (R ⁶ ) ₂ O] _h Si (R ⁶ ) ₃
(In the formula, R ⁶ independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, f is 0 to 200, preferably an integer of 3 to 120, g is 1 to 10, preferably an integer of 1 to 5, h is an integer of 0 to 200, preferably an integer of 3 to 110.)

In the above formula, the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁶ has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples thereof preferably include those of the same type as those other than the aryl group and the aralkyl group among those exemplified as the group bonded to the silicon atom other than the alkenyl group, but the light resistance and heat resistance of the cured product can be mentioned. From the point of view, it is more preferably an alkyl group, particularly preferably a methyl group.

（式中、括弧内のシロキサン単位は、任意の配列順でよい。）
（Ａ）成分は、一種単独で用いても二種以上を併用してもよい。 Specific examples of the component (A) include those represented by the following formulas.

(In the formula, the siloxane unit in parentheses may be in any sequence order.)
The component (A) may be used alone or in combination of two or more.

[(B) component]
The component (B) is a branched organopolysiloxane represented by the following average unit formula (1).
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ¹ R ² SiO) _n (R ² ₂ SiO) _p (R ¹ SiO _3/2 ) _q (R ² SiO) _3/2 ) _r (SiO _4/2 ) _s (1)
(In the formula, R ¹ independently represents an alkenyl group and R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, at least 80 of all R ² . Mol% is a methyl group and l, m, n, p, q, r and s are l ≧ 0, m ≧ 0, n ≧ 0, p ≧ 0, q ≧ 0, r ≧ 0 and s, respectively. It is a number that satisfies ≧ 0, but is a number that satisfies m + n + q> 0, q + r + s> 0, and l + m + n + p + q + r + s = 1).

The component (B) is a branched organopolysiloxane having a branched structure such as R ¹ SiO _3/2 unit or SiO _4/2 unit. Further, the component (B) is waxy or solid at 25 ° C., and “waxic” indicates almost self-fluidity at 25 ° C. of 10,000 Pa · s or more, particularly 100,000 Pa · s or more. It means that it is not gum-like (raw rubber-like).

In the above average composition formula (1), the alkenyl group represented by R ¹ is the same as that exemplified as the alkenyl group bonded to the silicon atom in the component (A), but is easily available and priced. From the aspect, a vinyl group is preferable.

Addition reactive carbon represented by R ² - 1 monovalent hydrocarbon radical unsubstituted or substituted without any carbon double bond, and those exemplified as groups bonded to silicon atoms other than alkenyl groups in component (A) Although of the same type, at least 80 mol% (80-100 mol%) of total R ² is a methyl group. When the proportion of methyl groups is less than 80 mol% of the total R ² , the compatibility with the component (A) is inferior, so that the composition becomes cloudy and the desired highly transparent cured product can be obtained. Sometimes not.

l is 0 to 0.65, m is 0 to 0.65, n is 0 to 0.5, p is 0 to 0.5, q is 0 to 0.8, r is 0 to 0.8, and s is 0 to 0.8. The number is preferably 0 to 0.6. Further, m + n + q is preferably 0.1 to 0.8, particularly 0.2 to 0.65, and q + r + s is 0.1 to 0.8, particularly 0.2 to 0.6. Is preferable.

The content of the alkenyl group bonded to the silicon atom in the component (B) is preferably in the range of 0.01 to 1 mol, preferably in the range of 0.05 to 0.5 mol, per 100 g of the component (B). Is more preferable. When the content of the alkenyl group satisfies the range of 0.01 to 1 mol, the crosslinking reaction proceeds sufficiently and a cured product having a higher hardness can be obtained.

Specific examples of such component (B) include organopolysiloxane represented by the following average unit formula.
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (SiO _4/2 ) _s
(R ¹ R ² ₂ SiO _1/2 ) _m (SiO _4/2 ) _s
(R ¹ R ² SiO) _n (R ² ₂ SiO) _p (R ² SiO _3/2 ) _r
(R ¹ R ² ₂ SiO _1/2 ) _m (R ² ₂ SiO) _p (R ¹ SiO _3/2 ) _q
(R ¹ R ² ₂ SiO _1/2 ) _m (R ² ₂ SiO) _p (R ² SiO _3/2 ) _r
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ² ₂ SiO) _p (R ² SiO _3/2 ) _r
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ² ₂ SiO) _p (R ¹ R ² SiO) _n (R ² SiO _3/2 ) _r
(In the formula, R ¹ , R ² , l, m, n, p, q, r and s are the same as described above.)

Specific examples of the component (B) include organopolysiloxane represented by the following average unit formula.
(Me ₃ SiO _1/2 ) _0.4 (ViMe ₂ SiO _1/2 ) _0.1 (SiO _4/2 ) _{0.5
(ViMeSiO) 0.4 (Me 2 SiO} ) 0.15 (MeSiO 3/2) 0.45
(ViMe ₂ SiO _1/2 ) _0.2 (Me ₂ SiO) _0.25 (MeSiO _3/2 ) _0.55

In the present invention, the ratio of the component (B) to the component (A) is also important, and the content of the component (B) is (B) with respect to a total of 100 parts by mass of the component (A) and the component (B). The amount of the component is 50 to 90 parts by mass, preferably 60 to 80 parts by mass, and more preferably 70 to 80 parts by mass. If the content of the component (B) is less than 50 parts by mass, the target high hardness may not be obtained, and if it exceeds 90 parts by mass, the viscosity of the composition becomes significantly high, and the composition It becomes difficult to use an object as a die bond material for an LED element or the like.
The component (B) may be used alone or in combination of two or more.

[Component (C)]
The component (C) is represented by the following average unit formula (2), has at least two SiH bonds in one molecule, and 20% or more of the SiO _2/2 units in the component (C) is R. ³ is a linear or cyclic organohydrogenpolysiloxanes are ₂ SiO _2/2 units. The component (C) is a component that acts as a cross-linking agent that reacts with the alkenyl group contained in the above-mentioned components (A) and (B) by a hydrosilylation reaction to crosslink.
R ³ _a H _b SiO _{(4-ab) / 2} (2)
(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, and at least 50 mol% of the total R ³ is a methyl group, a and b is a number that satisfies 1.2 ≦ a ≦ 2.1, 0.1 ≦ b ≦ 1.0, and 1.6 ≦ a + b ≦ 2.4.)

From the viewpoint that the component (C) is a component that acts as a cross-linking agent, the viscosity of the component (C) is preferably 1,000 mPa · s or less at 25 ° C., more preferably 0.5 to 1,000 mPa · s. , More preferably 2 to 200 mPa · s.

Further, from the viewpoint of the balance of cross-linking, the content of the component (C) is such that the number of SiH bonds in the component (C) is 0.5 with respect to one alkenyl group of the components (A) and (B). The amount is ~ 5.0, preferably 0.7 to 3.0.

In the component (C), SiH contained in one molecule at least 2 (usually 2 to 200), preferably 3 or more (for example, 3 to 100), more preferably about 4 to 50. The bond may be located at either the end of the molecular chain or in the middle of the molecular chain, or may be located at both of them.

The content of the SiH bond in the component (C) is preferably in the range of 0.001 to 0.02 mol, more preferably in the range of 0.002 to 0.017 mol, per 1 g of the component (C). ..

Further, the molecular structure of the component (C) may be any of a linear, cyclic, branched, and three-dimensional network structure. The number (or degree of polymerization) of silicon atoms in one molecule of the component (C) is preferably 2 to 200, more preferably 3 to 100, and even more preferably about 4 to 50.

In the above average composition formula (2), R ³ is an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, and is bonded to a silicon atom other than the alkenyl group in the component (A). Although those were the same as those exemplified as the organic group, at least 50 mole% of the total R ^3, preferably 60 to 100 mol% are methyl groups. If the proportion of methyl groups is less than 50 mole% of the total R ³ is, (A) is inferior in compatibility with the component and the component (B), if the problem of cloudiness or composition or phase separation occurs There is.

It is preferable that a is 1.2 to 2.0, b is 0.2 to 1.0, and a + b is 1.8 to 2.2.

Examples of the organohydrogenpolysiloxane represented by the average composition formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and Tris ( Hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane, both-terminal Trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, both-terminal dimethylhydrogensiloxy group-blocking dimethylpolysiloxane, both-terminal dimethylhydrogensiloxy group-blocking methylhydrogenpolysiloxane, both-terminal dimethylhydrogensiloxy group-blocking dimethyl Siloxane / methylhydrogensiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-terminal trimethyl Syroxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both-terminal dimethylhydrogen siloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both-terminal dimethylhydrogensiloxy group-blocked methylhydro Gensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit copolymer, (CH ₃₎ ) A copolymer consisting of ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and (C ₆ H ₅ ) ₃ SiO _1/2 units Examples thereof include a copolymer composed of.

Specific examples of the component (C) include a linear organohydrogenpolysiloxane represented by the following formula and a cyclic organohydrogenpolysiloxane.
Me ₃ SiO (MeHSiO) _i (Me ₂ SiO) _j SiMe ₃
(In the formula, i is an integer of 2 to 100 and j is an integer of 1 to 100.)

（式中、括弧内のシロキサン単位は、任意の配列順でよい。）
（Ｃ）成分は、一種単独で用いても二種以上を併用してもよい。

(In the formula, the siloxane unit in parentheses may be in any sequence order.)
The component (C) may be used alone or in combination of two or more.

[(D) component]
The component (D) is a platinum group metal-based catalyst, and the component (D) is used as a reaction catalyst for promoting the reaction (hydrosilylation reaction) between the above-mentioned components (A) and (B) and (C). It is a working ingredient.

As the platinum group metal-based catalyst, any catalyst known as a hydrosilylation reaction catalyst can be used. For example, platinum black, rhodium, platinum group metal simple substance such as _{palladium; H 2 PtCl 4 · kH 2} O, H 2 PtCl 6 · kH 2 O, NaHPtCl 6 · kH 2 O, KHPtCl 6 · kH 2 O, Na 2 PtCl ₆ · kH ₂ O, K ₂ PtCl ₄ · kH ₂ O, PtCl ₄ · kH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · kH ₂ O (in the formula, k is an integer from 0 to 6, preferably 0. Platinum chloride, chloroplatinic acid, and chloroplatinate such as (or 6); alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972); complex of chloroplatinic acid and olefin (US). (See Patents No. 3,159,601, No. 3,159,662, No. 3,775,452); Platinum group metals such as platinum black and palladium are made of alumina, silica, and carbon. Platinum chloride, chloroplatinic acid, or chloroplatinate and vinyl group-containing siloxane, especially vinyl group-containing cyclics; chlorodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); Examples include a complex with siloxane. Among these, preferred ones include those obtained by silicone-modifying platinum chloride acid from the viewpoint of compatibility and chlorine impurities. Specifically, for example, platinum chloride modified with tetramethylvinyldisiloxane. Examples include catalysts.

The content of the component (D) is a so-called effective amount, specifically, 1 to 500 ppm, preferably 3 to 100 ppm, in terms of mass of metal atoms, based on the total of the components (A) to (C). The amount is preferably 5 to 40 ppm.

[Other ingredients]
In addition to the above components (A) to (D), the silicone resin composition for die bonding of the present invention may contain other components exemplified below, if necessary. Other components include, for example, a thioxane control agent such as fumed silica; a light scattering agent such as crystalline silica; a reinforcing material such as fumed silica and crystalline silica; a phosphor; a petroleum solvent, a reactive functional group. A viscosity modifier such as non-reactive silicone oil that does not have a carbon functional silane, an epoxy group, an alkoxy group, a hydrogen atom bonded to a silicon atom (that is, a SiH bond), and an alkenyl group such as a vinyl group bonded to a silicon atom. Adhesion improvers such as silicone compounds other than the components (A) to (D) having at least one of the above; conductivity-imparting agents such as metal powders such as silver and gold; pigments and dyes for coloring; ethynylcyclohexanol, Examples thereof include reaction inhibitors such as tetramethyltetravinyltetracyclosiloxane. These other components may be used alone or in combination of two or more.

<Cured product>
Furthermore, the present invention provides a cured product of the above-mentioned silicone resin composition for die bonding.
The silicone resin composition for die bonding of the present invention may be cured under known conditions, for example, by heating at 60 to 180 ° C. for 10 minutes to 3 hours. In particular, the shore D hardness of the cured product obtained by curing the composition is preferably 50 or more. The curing condition for setting the shore D hardness to 50 or more is usually to heat and cure the silicone resin composition for die bonding of the present invention at 100 to 180 ° C. for 30 minutes to 180 minutes.
The cured product of the silicone resin composition for die bonding of the present invention has a small amount of volatile matter during curing, so that the gold pad is not contaminated, and the hardness is higher, so that it is particularly used for die bonding of LED elements and the like. It is useful as a die bond material. For example, the volatile content of the composition of the present invention when cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours can be 1.5% by mass or less.

<Light emitting diode element>
Furthermore, the present invention provides a light emitting diode element that is die-bonded with the cured product.
As an example of a method of die bonding an optical element (for example, a light emitting diode) using the die bonding silicone resin composition of the present invention, the die bonding silicone resin composition of the present invention is filled in a syringe and a dispenser is used. After coating on a substrate such as a package to a thickness of 5 to 100 μm in a dry state, an optical element is arranged on the coated composition, and the composition is cured to place the optical element on the substrate. Examples include a method of die bonding. Further, the composition is placed on a squeegee dish, and while squeezing, the composition is applied onto the substrate in a dry state to a thickness of 5 to 100 μm by a stamping method, and then an optical element is arranged on the applied composition. The optical element may be die-bonded onto the substrate by curing the optical element. The curing conditions of the composition may be as described above. In this way, a highly reliable light emitting diode element die-bonded with the cured product of the silicone composition for die bonding of the present invention can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "Me" represents a methyl group and "Vi" represents a vinyl group. The viscosity is a value at 25 ° C. using a rotational viscometer.

[Synthesis Example 1]
Synthesis of component (D): The reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane was averaged so that the platinum content was 0.04% by mass. Formula: ViMe ₂ SiO (Me ₂ SiO) ) A platinum catalyst was prepared by diluting with linear dimethylpolysiloxane (viscosity 60 mPa · s) represented by ₄₀ SiMe ₂ Vi.

[Example 1]
Average molecular formula: ViMe ₂ SiO (SiMe ₂ O) ₄₀ A linear dimethylpolysiloxane (A-1) represented by SiMe ₂ Vi and having a viscosity of 60 mPa · s at 25 ° C. with both ends sealed with vinyl groups. And, it is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 , and SiO _4/2 units, and the molar ratio of Me ₃ SiO _1/2 and ViMe ₂ SiO _1/2 to SiO _4/2 is A ratio of 25:75 by mass ratio of a solid silicone resin (B) to a xylene solution of a solid silicone resin (B) at 25 ° C. at 0.8 and a vinyl group amount of 0.085 mol / 100 g with respect to a solid content. Mixed in. Xylene was removed from this mixture at 160 ° C. under a reduced pressure of 10 mmHg or less to obtain a mixed liquid of polysiloxane.
Next, 16.6 parts by mass of methylhydrogensiloxane (C-1) represented by the average molecular formula: Me ₃ SiO (MeHSiO) ₄₅ (Me ₂ SiO) ₁₇ SiMe ₃ in 100 parts by mass of the mixed liquid of this polysiloxane. As other components, 5 parts by mass of an epoxy group-containing cyclic organopolysiloxane (F-1) represented by the following formula, and 3 parts by mass of tetramethyltetravinyltetracyclosiloxane (G-1) as an addition reaction control agent. 2.4 parts by mass of triallyl isocyanurate (G-2) was mixed to obtain a transparent liquid (the molar ratio of total SiH groups to total alkenyl groups in the composition was 1.3).

Further, 3 parts by mass of the component (D) obtained in Synthesis Example 1 and 5 parts by mass of fumed silica: Leoloseal DM-30S (E) manufactured by Tokuyama Co., Ltd. are mixed with 100 parts by mass of this liquid. A transparent silicone resin composition for die bonding having a viscosity at ° C. of 23 Pa · s was obtained.

[Example 2]
Average molecular formula: ViMe ₂ SiO (SiMe ₂ O) ₄₀ A linear dimethylpolysiloxane (A-1) represented by SiMe ₂ Vi and having a viscosity of 60 mPa · s at 25 ° C. with both ends sealed with vinyl groups. And, it is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 , and SiO _4/2 units, and the molar ratio of Me ₃ SiO _1/2 and ViMe ₂ SiO _1/2 to SiO _4/2 is A ratio of 25:75 by mass ratio of a solid silicone resin (B) to a xylene solution of a solid silicone resin (B) at 25 ° C. at 0.8 and a vinyl group amount of 0.085 mol / 100 g with respect to a solid content. Mixed in. Xylene was removed from this mixture at 160 ° C. under a reduced pressure of 10 mmHg or less to obtain a mixed liquid of polysiloxane.

Then, the mixture 100 parts by weight liquid polysiloxane, the average molecular _{formula: Me 3 SiO (SiHMeO) 66} (SiMe 2 O) 32 methylhydrogensiloxane represented by the SiMe ₃ (C-2) 17.5 parts by weight As other components, 5 parts by mass of the epoxy group-containing cyclic organopolysiloxane (F-1) represented by the above formula, and 3 parts by mass of tetramethyltetravinyltetracyclosiloxane (G-1) as an addition reaction control agent. 2.4 parts by mass of triallyl isocyanurate (G-2) was mixed to obtain a transparent liquid (the molar ratio of total SiH groups to total alkenyl groups in the composition was 1.3).

Further, 3 parts by mass of the component (D) obtained in Synthesis Example 1 and 5 parts by mass of fumed silica: Leoloseal DM-30S (E) manufactured by Tokuyama Co., Ltd. are mixed with 100 parts by mass of this liquid. A transparent silicone resin composition for die bonding having a viscosity of 27 Pa · s was obtained.

[Example 3]
Average molecular formula: ViMe ₂ SiO (SiMe ₂ O) ₁₀ A linear dimethylpolysiloxane (A-2) represented by SiMe ₂ Vi and having a viscosity of 10 mPa · s at 25 ° C. with both ends sealed with vinyl groups. And, it is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 , and SiO _4/2 units, and the molar ratio of Me ₃ SiO _1/2 and ViMe ₂ SiO _1/2 to SiO _4/2 is A ratio of 25:75 by mass ratio of a solid silicone resin (B) to a xylene solution of a solid silicone resin (B) at 25 ° C. at 0.8 and a vinyl group amount of 0.085 mol / 100 g with respect to a solid content. Mixed in. Xylene was removed from this mixture at 160 ° C. under a reduced pressure of 10 mmHg or less to obtain a mixed liquid of polysiloxane.

Then, the mixture 100 parts by weight liquid polysiloxane, the average molecular _{formula: Me 3 SiO (SiHMeO) 66} (SiMe 2 O) 32 methylhydrogensiloxane represented by the SiMe ₃ (C-2) 17.7 parts by weight And 1.2 parts by mass of epoxy group-containing organopolysiloxane (F-2) represented by the following formula as other components, and 3 parts by mass of tetramethyltetravinyltetracyclosiloxane (G-1) as an addition reaction control agent. And 2.4 parts by mass of triallyl isocyanurate (G-2) were mixed to obtain a transparent liquid (the molar ratio of total SiH groups to total alkenyl groups in the composition was 1.3).

Further, 3 parts by mass of the component (D) obtained in Synthesis Example 1 and 8 parts by mass of fumed silica: Leoloseal DM-30S (E) manufactured by Tokuyama Co., Ltd. are mixed with 100 parts by mass of this liquid. A transparent silicone resin composition for die bonding having a viscosity at 25 ° C. of 34 Pa · s was obtained.

[Comparative Example 1]
Instead of 16.6 parts by mass of (C-1) in Example 1, 10 parts by mass of methylhydrogensiloxane (C-3) represented by the average molecular formula: Me ₃ SiO (SiHMeO) ₈ SiMe ₃ was used. The same operation as in Example 1 was carried out to obtain a transparent addition-curable silicone resin composition having a viscosity of 35 Pa · s.

[Comparative Example 2]
Instead of (C-2) 17.7 parts by mass of Example 3, 8.7 parts by mass of methylhydrogensiloxane (C-4) represented by the average molecular formula: Me ₃ SiO (SiHMeO) ₃₈ SiMe ₃ is used. The same operation as in Example 3 was carried out except for the above, to obtain a transparent addition-curable silicone resin composition having a viscosity of 38 Pa · s.

[Comparative Example 3]
Example 1 (C-1) in place of 16.6 parts by weight, the average molecular _{formula: Me 3 SiO (SiHMeO) 7} (SiMe 2 O) 1 methylhydrogensiloxane represented by the SiMe ₃ (C-5) 13 The same operation as in Example 1 was carried out except that 4 parts by mass was used to obtain a transparent addition-curable silicone resin composition having a viscosity of 38 Pa · s.

The following tests were carried out on the compositions prepared as described above. The test results are shown in Table 1.
(Measurement of hardness of cured product)
Using the compositions obtained in each Example and each Comparative Example, the Shore D hardness of the cured product obtained by heating at 150 ° C. for 3 hours was measured.

(Volatile content during curing)
1.0 g of the composition obtained in each Example and each Comparative Example was spread on an aluminum petri dish of 60 mmφ, and after 100 ° C. × 1 hour, it was heat-cured at 150 ° C. × 2 hours. From the mass change before and after curing, the volatile matter at the time of curing was calculated according to the following formula.
(% of volatile matter at the time of curing) = 100-((mass after curing) ÷ (mass before curing) x 100)

(Gold pad contamination)
An LED element provided with a gold pad is placed on a slide glass, and 4 g of the die bonding silicone resin composition obtained in each example and the addition-curable silicone resin composition obtained in each comparative example are arranged around the slide glass. .. After putting it in a container and curing it at 80 ° C for 2 hours under a semi-sealed state, and then curing it at 100 ° C for 1 hour and then at 150 ° C for 2 hours, the contamination status of the gold pad was observed with a microscope, and contamination occurred. Those that did not do so were described as "GOOD", and those that were contaminated were described as "NG".

As shown in Table 1, the silicone resin composition for die bonding of the present invention gives a cured product having a high hardness and has a small amount of volatile matter during curing, so that the gold pad is not contaminated and is good. On the other hand, in Comparative Examples 1 to 3 using the organohydrogenpolysiloxane outside the range of the component (C) of the present invention, although a cured product having a high hardness was given, contamination of the gold pad occurred.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same action and effect is the present invention. Is included in the technical scope of.

Claims (3)

(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a viscosity at 25 ° C. of less than 100 mPa · s.
(B) Branched organopolysiloxane represented by the following average unit formula (1) and waxy or solid at 25 ° C.: (B) with respect to a total of 100 parts by mass of the components (A) and (B). Amount of ingredients 50-90 parts by mass,
(R ² ₃ SiO _1/2 ) _l (R ¹ R ² ₂ SiO _1/2 ) _m (R ¹ R ² SiO) _n (R ² ₂ SiO) _p (R ¹ SiO _3/2 ) _q (R ² SiO) _3/2 ) _r (SiO _4/2 ) _s (1)
(In the formula, R ¹ independently represents an alkenyl group and R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, at least 80 of all R ² . Mol% is a methyl group and l, m, n, p, q, r and s are l ≧ 0, m ≧ 0, n ≧ 0, p ≧ 0, q ≧ 0, r ≧ 0 and s, respectively. It is a number that satisfies ≧ 0, m + n + q> 0, q + r + s> 0, and satisfies l + m + n + p + q + r + s = 1.)
Represented by (C) the following average compositional formula (2), having at least two SiH bonds per molecule, and, (C) more than 20% of _{SiO 2/2} units in component ^R ₃ 2 SiO Linear or cyclic organohydrogenpolysiloxane which is _2/2 unit: SiH bond in component (C) is 0.5 to 5 for one silicon atom-bonded alkenyl group in component (A) and component (B). Amount of 0.0 pieces,
R ³ _a H _b SiO _{(4-ab) / 2} (2)
(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no addition-reactive carbon-carbon double bond, and at least 50 mol% of the total R ³ is a methyl group, and a and b is a number that satisfies 1.2 ≦ a ≦ 2.1, 0.1 ≦ b ≦ 1.0, and 1.6 ≦ a + b ≦ 2.4), and (D) a platinum group metal-based catalyst. : Contains an amount of 1 to 500 ppm in terms of mass of metal atoms with respect to the total of the components (A) to (C).
A silicone resin composition for die bonding, which has a volatile content of 1.5% by mass or less when cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours. A cured product obtained by curing the silicone resin composition for die bonding according to claim 1. A light emitting diode element characterized by being die-bonded with the cured product according to claim 2.